CN113970801B - Photonic crystal material and preparation method and application thereof - Google Patents
Photonic crystal material and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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Abstract
The invention discloses a photonic crystal material, which comprises an inner layer and a surface layer positioned on one surface of the inner layer, wherein the inner layer is arranged on the surface of the inner layer; the inner layer comprises a micro-nano hole array which is arranged periodically and a filling material filled between the holes; the surface layer includes irregular holes and a filler filled between the holes. The structural color of the photonic crystal material can be reversibly changed under the illumination condition. The invention also discloses a preparation method and application of the photonic crystal material.
Description
Technical Field
The invention relates to the field of intelligent high polymer materials. More particularly, to a photonic crystal material, a preparation method and application thereof.
Background
The photonic crystal has special light manipulation characteristics due to a unique periodic structure, and has potential application prospects in the aspects of rapid sensing, trace detection, outdoor coating, novel optical devices and the like. The patterned photonic crystal provides a new way for constructing high-performance optical devices with unique structures and functions, and is widely applied to the fields of sensors, displays, anti-counterfeiting technologies and the like.
Over the past few decades, several methods have been developed for preparing patterned photonic crystals: substrate induced assembly, inkjet printing, regioselective immobilization/modification, and the like. For example, patterned substrates with microstructural or wettability differences can induce assembly of colloidal particles, forming ordered photonic crystal dots or lines. Similarly, inkjet printing of colloidal particle dispersions (e.g., polystyrene) is also an effective method of preparing patterned photonic crystals. However, patterned photonic crystals made by self-assembly/inkjet printing are unresponsive. Further, a responsive patterned photonic crystal is prepared by selective region immobilization under an external stimulus (e.g., magnetic/electric field). However, such responsive patterned photonic crystals are an irreversible process once immobilized. In addition, some special methods such as hot pressing, lithography, and ion doping/dedoping have been developed as new methods for preparing patterned photonic crystals. However, patterned photonic crystals reported in previous studies are mostly irreversible or slowly reversible processes and require complex external conditions. Therefore, the preparation of patterned photonic crystals with fast rewritable/erasable characteristics has attracted a lot of attention.
Clearly, dynamic materials are a necessary condition for constructing reversibly patterned photonic crystals. Accordingly, there is a need to provide a new photonic crystal material to enable the preparation and application of a responsive reversibly patterned photonic crystal.
Disclosure of Invention
Based on the above drawbacks, a first object of the present invention is to provide a photonic crystal material, the structural color of which can be reversibly changed under illumination conditions.
The second object of the present invention is to provide a method for preparing a photonic crystal material.
A third object of the present invention is to provide a photonic crystal material for use.
In order to achieve the first object, the present invention adopts the following technical scheme:
a photonic crystal material, wherein the structure of the photonic crystal material comprises an inner layer and a surface layer positioned on one surface of the inner layer;
wherein the inner layer and the surface layer both comprise a micro-nano hole array which is periodically arranged and a filling material filled between the holes;
the surface layer includes irregular holes and a filler filled between the holes.
Further, the diameter of the holes in the skin layer is smaller than the diameter of the holes in the inner layer.
Further, the inner layer of the photonic crystal material has an inverse opal structure.
Further, the filling material comprises azobenzene polymer; preferably, the azobenzene polymer is selected from an aromatic azobenzene polymer or an aliphatic azobenzene polymer.
Further, the azobenzene polymer is obtained by carrying out illumination polymerization on a raw material mixed system consisting of azobenzene monomers, a cross-linking agent and a photoinitiator; wherein the cross-linking agent contains an azo-phenyl group in its structure.
Further, in the inner layer, the radial dimension of the micro-nano holes is 150-300nm, and in the hole array, the distance between adjacent holes is 10-50nm.
In order to achieve the second object, the present invention provides the following technical solutions:
a preparation method of a photonic crystal material comprises the following steps:
providing a photonic crystal template;
forming the photonic crystal material on a photonic crystal template;
and removing the photonic crystal template to obtain the photonic crystal material.
Further, the method for forming the photonic crystal material on the photonic crystal template comprises the following steps: spin-coating a raw material mixed system comprising an azobenzene monomer, a cross-linking agent and a photoinitiator on the surface of the photonic crystal template, and polymerizing by illumination to obtain the photonic crystal material; wherein the cross-linking agent contains an azo-phenyl group in its structure.
Further, the photonic crystal template consists of a substrate and silicon dioxide microspheres assembled on the surface of the substrate by adopting a vertical deposition method.
To achieve the third object, the present invention provides the use of the photonic crystal material as described in the first object above in the fields of erasable photonic crystal paper, remote writing board/smart window.
The beneficial effects of the invention are as follows:
in the photonic crystal material provided by the invention, the structural color of the photonic crystal material is reversibly converted under the illumination condition due to the specific structure and material, so that the photonic crystal material is a photoresponsive reversible patterning photonic crystal. The photonic crystal material has potential application prospect in the field of preparation of dynamic patterning photonic crystals.
In the preparation method of the photonic crystal material provided by the invention, the photonic crystal material with uniform structure can be obtained by adopting a spin coating preparation method preferably. The preparation method is simple, low in cost and suitable for large-scale preparation.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 shows a scanning electron microscope picture of the photonic crystal material prepared in example 1.
Fig. 2 shows the reversible structural color-transformation of the photonic crystal material of example 2 under illumination.
FIG. 3 shows that example 3 produces a rewritable pattern on the surface of a photonic crystal material.
Fig. 4 shows example 4 for preparing a remote tablet/smart window using photonic crystal material.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
According to one embodiment of the present invention, there is provided a photonic crystal material having a structure including an inner layer and a surface layer located on one surface of the inner layer;
wherein the inner layer and the surface layer both comprise a micro-nano hole array which is periodically arranged and a filling material filled between the holes;
the surface layer includes irregular holes and a filler filled between the holes.
In this embodiment, the inner layer preferably has a layer structure having one or more layers, and each layer in the layer structure includes the periodically arranged micro-nano-scale hole array and a filling material filled between the holes. The outer layer is preferably a layer.
Further, the inner layer of the photonic crystal material has an inverse opal structure.
Further, the packing material comprises an azobenzene polymer. That is, the photonic crystal material contains an azobenzene polymer therein. The azobenzene polymer suitable for use in embodiments of the present invention is selected from aromatic azobenzene polymers or aliphatic azobenzene polymers. Specifically, aromatic azobenzene polymers include, but are not limited to, A6AB6/DA6AB and the like. Aliphatic azobenzene polymers include, but are not limited to, A6AB6/DA6AB and the like.
Wherein, the structural formula of A6AB6 is shown as the following formula:
wherein, the structural formula of DA6AB is shown as the following formula:
in a preferred scheme, the azobenzene polymer is obtained by carrying out illumination polymerization on a raw material mixed system comprising azobenzene monomers, a cross-linking agent and a photoinitiator; wherein the cross-linking agent contains an azo-phenyl group in its structure. Exemplary cross-linking agents include, but are not limited to, DA6AB and the like. In the research process, the invention discovers that the obtained photonic crystal material has larger red shift degree under the illumination condition by adopting the cross-linking agent containing the azo-phenyl group in the structure. The reason is hypothesized to be that each molecule in the material structure may isomerise under uv light, resulting in a large change in refractive index and a correspondingly large degree of red-shift.
In a preferred embodiment, the diameter of the holes in the skin layer is smaller than the diameter of the holes in the inner layer. Such a structure is also advantageous in that the resulting photonic crystal material has a greater degree of red shift under light conditions. The reason is that this particular structure allows an additional greater content of azobenzene polymer to be in the illuminated region upon irradiation with ultraviolet light, resulting in a larger change in refractive index and a corresponding larger degree of red-shift.
In a preferred embodiment, the radial dimension of the micro-nano holes in the inner layer is 150-300nm, and the distance between adjacent holes in the hole array is 10-50nm. Further, for example, the micro-nano-scale pores may also have a radial dimension of, but are not limited to, 160-290nm, 170-280nm, 180-270nm, 190-260nm, 200-250nm, 210-240nm, etc.; the adjacent hole spacing may also be, but is not limited to, 12-45nm, 14-40nm, 16-35nm, 18-30nm, 20-25nm, etc.
In a preferred embodiment, the holes in both the inner and outer layers are pit-shaped.
In a preferred embodiment, the photonic crystal material has a thickness of 5-40um. Further, for example, the photonic crystal structure may also have a thickness of, but not limited to, 6-19um, 7-18um, 8-17um, 9-16um, 10-15um, etc.
According to still another embodiment of the present invention, there is provided a method for preparing a photonic crystal material, the method comprising the steps of:
providing a photonic crystal template;
forming the photonic crystal material on a photonic crystal template;
and removing the photonic crystal template to obtain the photonic crystal material.
Further, a raw material mixed system comprising an azobenzene monomer, a cross-linking agent and a photoinitiator is applied to a photonic crystal template, and the photonic crystal material is obtained through photo-polymerization, wherein the cross-linking agent contains an azobenzene group in the structure.
Further, the photonic crystal material is formed on a photonic crystal template by a spin-coating post-illumination method. By this method, a structure as described in the present invention can be obtained, in particular such that the diameter of the holes in the surface layer is smaller than the diameter of the holes in the inner layer in the resulting structure. Thereby being more beneficial to improving the red shift degree under the illumination condition.
Illustratively, the method of forming the photonic material specifically includes the steps of:
spin-coating a raw material mixed system comprising an azobenzene monomer, a cross-linking agent and a photoinitiator on the surface of the photonic crystal template, and polymerizing by illumination to obtain the photonic crystal material; wherein the cross-linking agent contains an azo-phenyl group in its structure.
Illustratively, the azobenzene monomer described above includes, but is not limited to, one selected from A6AB6, and the like.
Illustratively, the above-described crosslinking agents include, but are not limited to, those selected from DA6AB and the like.
Illustratively, the above-described photoinitiators include, but are not limited to, those selected from the group consisting of photoinitiator 784, photoinitiator 276, and the like. Wherein the structural formula of the photoinitiator 784 is shown as follows:
illustratively, the ratio of the amount of material of the above photoinitiator to the amount of material of the total azobenzene polymer is: 1-10:100.
Illustratively, the ratio of the amount of crosslinker material to the total azobenzene polymer material is 1-10:100.
Exemplary, the conditions of the illumination polymerization are: 1.5-3.5mW/cm 2 Light polymerization at 550nm for 1.5-3 hours.
Further, the photopolymerization in the present invention is preferably ultraviolet irradiation.
Further, the method for removing the photonic crystal template comprises the following steps: and (3) soaking and dissolving the photonic crystal template by adopting hydrofluoric acid with the mass fraction of 4%.
Further, the photonic crystal template consists of a substrate and silicon dioxide microspheres assembled on the surface of the substrate by adopting a vertical deposition method. Illustratively, the foregoing substrates include, but are not limited to, superhydrophilic solid substrates selected from common glass, quartz or silicon wafers. The super-hydrophilic solid substrate is used for facilitating the silicon dioxide microsphere to be assembled into a high-quality photonic crystal film on the surface of the silicon dioxide microsphere. The hydrofluoric acid with the mass fraction of 4% is selected, so that the rapid rate of dissolving the silicon dioxide microspheres is ensured, and the damage to the azobenzene polymer network can be avoided.
Further, the particle size of the silica microspheres is 150-300nm, and the silica microspheres with the particle size can be assembled into photonic crystal films with different band gaps in the visible light range, so that the azobenzene photonic crystal structures with different band gaps and inverse opal structures are prepared, the particle size of the microspheres is too large or too small, the assembly is difficult, and the band gaps of the assembled photonic crystal films are not suitable.
In a specific implementation process, the surfaces of the silica microspheres forming the photonic crystal template are provided with carboxyl groups, and the silica microspheres with the carboxyl groups are more favorable for compact arrangement in the assembly process, so that the photonic crystal template with better quality is formed. The preparation method of the silicon dioxide microsphere with carboxyl on the surface mainly adopts a method of hydrolyzing tetraethoxysilane in an alkaline environment, and comprises the following specific preparation methods:
1-2 parts by volume of deionized water and 19-22 parts by volume of ethanol are added to a round-bottomed flask, stirred and the system is kept constant between 28-35 ℃. Then adding 0.5-1.5 parts by volume of ammonia water to obtain a pre-reaction system. 2-2.5 parts by volume of ethanol and 1-1.8 parts by volume of ethyl orthosilicate are measured, preheated to 28-35 ℃, and then added into a pre-reaction system. Stirring and reacting for 5-15 hours to obtain the silica microsphere with carboxyl on the surface.
In addition, the photonic crystal material may be formed by photolithography.
According to yet another embodiment of the present invention, the present invention provides the use of a photonic crystal material as described above in the field of erasable photonic crystal paper, remote writing board/smart window.
In one example, the application specifically includes the steps of:
fixing the photonic crystal material on a substrate;
and (3) carrying out ultraviolet irradiation under the condition that the mask plate exists.
In the application method, after ultraviolet light irradiation, a photonic crystal pattern can be obtained.
Further, the application method further comprises the following steps:
adopting visible light to irradiate the pattern obtained after ultraviolet light irradiation, and enabling the pattern to disappear;
and changing the mask plates with different patterns, and performing ultraviolet irradiation.
By the application method, different photonic crystal patterns can be obtained.
In addition, according to actual situation needs, mask plates with different patterns can be selected and ultraviolet irradiation times can be carried out, so that the patterns with shape transformation can be obtained.
It should be noted that the photonic crystal material provided by the invention can generate reversible structural color transformation under illumination.
Exemplary, ultraviolet light (365 nm,120mW/cm 2 ) And irradiating the sample 2s through the photomask, and performing red shift on the structure of the irradiated area to form a photonic crystal pattern. Subsequently, the substrate was irradiated with visible light (560 nm,120mW/cm 2 ) The sample 2s was illuminated and the previously red-shifted areas of the structural color restored to the original structural color, so that the pattern disappeared. This process can be repeated to produce dynamic photonic crystal patterns and erasable photonic crystal papers. Meanwhile, the prepared pattern gradually disappears along with the increase of the observation angle, and has the peep-proof function.
The following describes the technical scheme of the present invention with reference to some specific embodiments:
example 1
Preparation of photonic crystal materials
Preparation of silica microspheres with carboxyl groups on the surface:
1.5 parts by volume of deionized water and 20.5 parts by volume of ethanol were added to the round-bottomed flask, stirred and the system was kept constant at between 30 ℃. Then, 1 part by volume of ammonia water was added to obtain a pre-reaction system. 2.3 parts by volume of a mixture of ethanol and 1.4 parts by volume of ethyl orthosilicate was measured, preheated to 30℃and then added to the pre-reaction system. Stirring and reacting for 8 hours to obtain the silica microsphere with carboxyl on the surface.
Preparation of a photonic crystal template:
and (3) diluting the 250nm silicon dioxide dispersion liquid with ethanol to be semitransparent, vertically placing the super-hydrophilic solid substrate in the silicon dioxide dispersion liquid, and keeping the temperature at 40 ℃ until the dispersion liquid is completely evaporated, so that the silicon dioxide microspheres can be self-assembled on the surface of the solid substrate to form the photonic crystal template with the band gap of about 630 nm.
Preparation of photonic crystal material:
(1) Treating the prepared photonic crystal template with the band gap of 630nm for 60s by using a plasma technology; (2) Spin-coating a mixed system of A6AB6/DA6AB (molar ratio 7:3) and a photoinitiator 784 on the surface of a photonic crystal template at 110 ℃, and then cooling the system to 88 ℃; (3) By 2mW/cm 2 Polymerizing under light of 550nm for 2 hours; (4) And (3) soaking and dissolving the photonic crystal template by using hydrofluoric acid with the mass fraction of 4% to obtain the photonic crystal material.
Scanning electron microscope results for photonic crystal materials
When the obtained photonic crystal material is subjected to a scanning electron microscope test, as shown in fig. 1, it can be found that the total thickness of the photonic crystal material is 10.8um, and the top is a structure with smaller pore diameter due to overfilling, but the inside of the sample presents a typical inverse opal structure, and the band gap and structural color of the sample appear depending on the photonic crystal structure inside. The radial dimension of the pit structure of the internal photonic crystal is 245nm, the distance between adjacent pits is 31nm, and in addition, the photonic crystal material is found to be a bright green structural color, and the photonic band gap is 540nm.
Example 2
Reversible structural color change under illumination
The photonic crystal material prepared in research example 1 has reversible structural color conversion under illumination, and the specific method comprises the following steps:
the photonic crystal material is stuck on a flat glass sheet by double-sided tape, ultraviolet light is irradiated under the condition that a mask exists to prepare a photonic crystal pattern, and the prepared pattern can be erased after being irradiated by visible light. And then changing masks with different shapes on the basis of the same film to prepare different photonic crystal patterns.
As shown in fig. 2. It was found that the irradiation with ultraviolet light (365 nm,120mW/cm 2 ) After 2s of photonic crystal materialThe structural color of the sample changes from purple to green, and the corresponding band gap is red shifted by 55nm. Subsequently, the substrate was irradiated with visible light (560 nm,120 mW/cm) 2 ) After 2s, the structural color of the sample was restored from green to the previous purple, and the corresponding band gap was blue shifted, as shown in fig. 2 (a, a'). Reversible structural color transitions can be achieved also for photonic crystal materials of different band gaps under illumination (fig. 2 (B, B').
Example 3
Preparation of dynamic photonic crystal pattern and erasable photonic crystal paper
The photonic crystal material prepared in example 1 can realize the preparation and erasure of different patterns on the surface of the same photonic crystal material through different masks, and is developed into erasable photonic crystal paper (fig. 3 (a, B)). The method comprises the following specific steps: 1. fixing the prepared azobenzene photonic crystal material on a base material; 2. ultraviolet light (365 nm,120 mW/cm) 2 ) Irradiating for 2s to obtain a photonic crystal pattern; 3. then irradiated with visible light (560 nm,120 mW/cm) 2 ) Illuminating the 2s erasable pattern; 4. and changing mask plates with different shapes on the surface of the same azobenzene photonic crystal material, and preparing a series of different photonic crystal patterns under the alternate irradiation of ultraviolet light/visible light. For example, FIG. 3 (A 1 -A 5 ) A series of skiing procedures are described. FIG. 3 (B) 1 -B 5 ) The letters "TI", the letter "TIPC", the letter "PC", the flowers and leaves, etc. FIG. 3 (C) 1 -C 2 ) Indicating that the minimum resolution of the prepared pattern can reach 35um. FIG. 3 (D) 1 -D 3 ) Is the institute of physics and chemistry of the Chinese academy. Meanwhile, the prepared pattern gradually disappears along with the increase of the observation angle, and has the peep-proof function.
Example 4
Preparation of remote writing board/intelligent window
The photonic crystal material prepared in example 1 can directly irradiate the surface of the photonic crystal material at a long distance through an ultraviolet laser pen, write any text or pattern, and then erase through irradiation of visible light, so as to develop a remote writing board (fig. 4 (a-C)). The method comprises the following specific steps: 1. to be prepared intoThe azobenzene photon crystal material is fixed on the base material; 2. ultraviolet laser pen (365 nm,120 mW/cm) 2 ) Focusing the light spots on the surface of the photonic crystal material, and then writing; 3. then irradiated with visible light (560 nm,120 mW/cm) 2 ) The erasable writing is irradiated. The ability of photonic crystal materials to selectively reflect light of a specific wavelength, and the property of reflecting light of different wavelengths by reversible transition between bandgaps, can be developed into smart windows where light selectively passes through (fig. 4 (D, E)). The method comprises the following specific steps: 1. fixing the prepared azobenzene photonic crystal material on a transparent substrate; 2. illuminating one side of the photonic crystal material with a light source of a specific wavelength while viewing from the other side; 3. by ultraviolet light (365 nm,120 mW/cm) 2 ) Irradiating the photonic crystal material 2s to change the structural color thereof; 4. illuminating one side of the photonic crystal material with a light source of the same wavelength while viewing from the other side; 5. irradiation with visible light (560 nm,120 mW/cm) 2 ) The photonic crystal material 2s is irradiated to restore its structural color.
Example 5
Preparation of photonic crystal materials
Preparation of silica microsphere with carboxyl on surface
1 part by volume of deionized water and 19 parts by volume of ethanol were added to a round-bottomed flask, stirred and the system was kept constant at between 28 ℃. Then, 0.5 parts by volume of aqueous ammonia was added to obtain a pre-reaction system. 2 parts by volume of a mixture of ethanol and 1 part by volume of ethyl orthosilicate was measured, preheated to 28℃and then added to the pre-reaction system. Stirring and reacting for 5 hours to obtain the silica microsphere with carboxyl on the surface.
Preparation of photonic crystal templates
And (3) diluting the 250nm silicon dioxide dispersion liquid with ethanol to be semitransparent, vertically placing the super-hydrophilic solid substrate in the silicon dioxide dispersion liquid, and keeping the temperature at 30 ℃ until the dispersion liquid is completely evaporated, so that the silicon dioxide microspheres can be self-assembled on the surface of the solid substrate to form the photonic crystal template with the band gap of about 630 nm.
Preparation of photonic crystal materials
(1) Treating the photonic crystal template with the band gap of 630nm for 20s by using a plasma technology; (2) Will A6ABThe mixed system of 6/DA6AB (molar ratio 9:1) and photoinitiator 784 was spin coated onto the photonic crystal template surface at 110 ℃, followed by cooling the system to 88 ℃; (3) With a power of 1.5mW/cm 2 Light polymerization at 550nm for 1.5 hours; (4) And (3) soaking and dissolving the photonic crystal template by using hydrofluoric acid with the mass fraction of 4% to obtain photonic crystal materials with different band gaps.
Example 6
Preparation of photonic crystal material with photonic crystal layer filled with silicon dioxide microspheres
Preparation of silica microsphere with carboxyl on surface
1 part by volume of deionized water and 19 parts by volume of ethanol were added to a round-bottomed flask, stirred and the system was kept constant at between 28 ℃. Then, 0.5 parts by volume of aqueous ammonia was added to obtain a pre-reaction system. 2 parts by volume of a mixture of ethanol and 1 part by volume of ethyl orthosilicate was measured, preheated to 28℃and then added to the pre-reaction system. Stirring and reacting for 5 hours to obtain the silica microsphere with carboxyl on the surface.
Preparation of photonic crystal templates
And (3) diluting the 250nm silicon dioxide dispersion liquid with ethanol to be semitransparent, vertically placing the super-hydrophilic solid substrate in the silicon dioxide dispersion liquid, and keeping the temperature at 30 ℃ until the dispersion liquid is completely evaporated, so that the silicon dioxide microspheres can be self-assembled on the surface of the solid substrate to form the photonic crystal template with the band gap of about 630 nm.
Preparation of photonic crystal materials
(1) Treating the photonic crystal template with the band gap of 630nm for 20s by using a plasma technology; (2) Spin-coating a mixed system of A6AB6/DA6AB (molar ratio 9:1) and a photoinitiator 784 on the surface of a photonic crystal template at 110 ℃, and then cooling the system to 88 ℃; (3) With a power of 1.5mW/cm 2 Polymerizing for 1.5 hours under 550nm illumination to obtain photonic crystal materials with different band gaps; (4) And (3) soaking and dissolving the photonic crystal template by using hydrofluoric acid with the mass fraction of 4% to obtain photonic crystal materials with different band gaps.
Examples 7 to 9
Preparation of photonic crystal materials
Preparation of silica microsphere with carboxyl on surface
1 part by volume of deionized water and 19 parts by volume of ethanol were added to a round-bottomed flask, stirred and the system was kept constant at between 28 ℃. Then, 0.5 parts by volume of aqueous ammonia was added to obtain a pre-reaction system. 2 parts by volume of a mixture of ethanol and 1 part by volume of ethyl orthosilicate was measured, preheated to 28℃and then added to the pre-reaction system. Stirring and reacting for 5 hours to obtain the silica microsphere with carboxyl on the surface.
Preparation of photonic crystal templates
And (3) diluting the 250nm silicon dioxide dispersion liquid with ethanol to the weight fractions of 0.5, 1.0 and 2.0wt% respectively, then vertically placing the super-hydrophilic solid substrate in the silicon dioxide dispersion liquid, and keeping the temperature at 30 ℃ until the dispersion liquid is completely evaporated, wherein the silicon dioxide microspheres can be self-assembled on the surface of the solid substrate to form the photonic crystal templates with the band gaps of about 630nm and the thicknesses of 5, 10 and 20 mu m respectively.
Preparation of photonic crystal materials
(1) Treating a photonic crystal template with a band gap of 630nm and thicknesses of 5, 10 and 20um respectively for 20s by using a plasma technology; (2) Spin-coating a mixed system of A6AB6/DA6AB (molar ratio 9:1) and a photoinitiator 784 on the surface of a photonic crystal template at 110 ℃, and then cooling the system to 88 ℃; (3) With a power of 1.5mW/cm 2 And (3) carrying out light polymerization at 550nm for 1.5 hours, and soaking and dissolving the photonic crystal template by using hydrofluoric acid with the mass fraction of 4% to obtain photonic crystal materials with different band gaps and photonic crystal structure thicknesses of 5, 10 and 20um respectively.
Examples 10 to 12
Preparation of photonic crystal materials
Preparation of silica microsphere with carboxyl on surface
1 part by volume of deionized water and 19 parts by volume of ethanol were added to a round-bottomed flask, stirred and the system was kept constant between 28 and 30 ℃. Then, 0.5 parts by volume of aqueous ammonia was added to obtain a pre-reaction system. 2 parts by volume of a mixture of ethanol and 1 part by volume of ethyl orthosilicate was measured, preheated to 28-30 ℃, and then added to the pre-reaction system. Stirring and reacting for 5 hours to obtain the silica microsphere with carboxyl groups on the surface and particle diameters of 300, 280 and 250 nm.
Preparation of photonic crystal templates
And (3) adding ethanol into the silica dispersion liquid with the particle diameters of 250, 280 and 300nm to dilute the silica dispersion liquid to be semitransparent, vertically placing the super-hydrophilic solid substrate in the silica dispersion liquid, and keeping the temperature at 30 ℃ until the dispersion liquid is completely evaporated, so that the silica microspheres can be self-assembled on the surface of the solid substrate to form the photonic crystal template with the band gaps of about 630, 700 and 750 nm.
Preparation of photonic crystal materials
(1) Treating the photonic crystal templates with band gaps of 630, 700 and 750nm for 20s by using a plasma technology; (3) Spin-coating a mixed system of A6AB6/DA6AB (molar ratio 9:1) and a photoinitiator 784 on the surface of a photonic crystal template at 110 ℃, and then cooling the system to 88 ℃; (4) With a power of 1.5mW/cm 2 And (3) carrying out light polymerization at 550nm for 1.5 hours, and soaking and dissolving the photonic crystal template by using hydrofluoric acid with the mass fraction of 4% to obtain photonic crystal materials with different band gaps and photonic crystal layer apertures of 230 nm, 250nm and 285nm respectively.
The photonic crystal materials prepared in examples 5 to 12 were examined for the transition of the reversible structure under light by the method as in example 2, and the results showed that the materials were irradiated with ultraviolet light (365 nm,120mW/cm 2 ) After 2s of photonic crystal material, the structural color of each example sample was changed, and the corresponding band gap was red shifted by at least 50nm or 55nm or 62nm. Subsequently, the substrate was irradiated with visible light (560 nm,120 mW/cm) 2 ) After 2s, the structural color of the sample reverted to the original color, and the corresponding band gap shifted blue.
The photonic crystal materials prepared in examples 5-12 were investigated for their use in the preparation of dynamic photonic crystal patterns and erasable photonic crystal papers, and in the preparation of remote writing tablets/smart windows, respectively, using the methods as in example 3 and example 4. The results were similar to those of example 3 and example 4.
Comparative example 1
Example 1 was repeated except that in the preparation step of the photonic crystal material, the spin coating method of step (2) was changed to "the photonic crystal template treated with plasma and the glass sheet having the polyimide alignment layer were assembled into a liquid crystal cell; and (3) filling the mixed system into a liquid crystal box at 110 ℃, then cooling the system to 88 ℃, and preparing the photonic crystal material under the same conditions.
Experiments were performed as in example 2, and it was found that the band gap red shift of the photonic crystal material was at most 30nm, which is far lower than the red shift levels achievable by the examples.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (6)
1. A photonic crystal material, characterized in that the structure of the photonic crystal material comprises an inner layer and a surface layer positioned on one surface of the inner layer;
the inner layer comprises a micro-nano hole array which is arranged periodically and a filling material filled between the holes;
the surface layer comprises irregular holes and filling materials filled among the holes;
the filling material comprises azobenzene polymer;
the azobenzene polymer is selected from aromatic azobenzene polymer or aliphatic azobenzene polymer;
the azobenzene polymer is obtained by carrying out illumination polymerization on a raw material mixed system consisting of azobenzene monomers, a cross-linking agent and a photoinitiator; wherein the structure of the cross-linking agent contains an azo phenyl group;
in the inner layer, the radial dimension of the micro-nano holes is 150-300nm, and in the hole array, the distance between adjacent holes is 10-50nm;
the diameter of the holes in the skin layer is smaller than the diameter of the holes in the inner layer.
2. The photonic crystal material of claim 1, wherein the inner layer of the photonic crystal material has an inverse opal structure.
3. A method of producing a photonic crystal material according to any one of claims 1 to 2, comprising the steps of:
providing a photonic crystal template;
forming the photonic crystal material on a photonic crystal template;
and removing the photonic crystal template to obtain the photonic crystal material.
4. A method of preparing a photonic crystal according to claim 3, wherein the method of forming the photonic crystal material on a photonic crystal template comprises the steps of: spin-coating a raw material mixed system comprising an azobenzene monomer, a cross-linking agent and a photoinitiator on the surface of the photonic crystal template, and polymerizing by illumination to obtain the photonic crystal material; wherein the cross-linking agent contains an azo-phenyl group in its structure.
5. The method according to claim 4, wherein the photonic crystal template comprises a substrate and silica microspheres assembled on the surface of the substrate by a vertical deposition method.
6. Use of a photonic crystal material according to any of claims 1-2 in the field of erasable photonic crystal paper, remote writing tablets/smart windows.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101655610A (en) * | 2009-09-11 | 2010-02-24 | 中国科学院长春应用化学研究所 | Preparation method of inverse opal hydrogel photonic crystal with hybridized structure |
| CN103103601A (en) * | 2011-11-10 | 2013-05-15 | 中国科学院化学研究所 | Method for preparing crack-free photonic crystal on surface of super-hydrophobic organism or super-hydrophobic imitation organism |
| CN103282387A (en) * | 2011-03-14 | 2013-09-04 | 旭化成化学株式会社 | Organic/inorganic composite, manufacturing method therefor, organic/inorganic composite film, manufacturing method therefor, photonic crystal, coating material, thermoplastic composition, microstructure, optical material, antireflection member, and optical lens |
| CN105384176A (en) * | 2015-11-04 | 2016-03-09 | 北京服装学院 | Prussian blue composite photonic crystal and preparing method and application thereof |
| CN109853040A (en) * | 2019-01-30 | 2019-06-07 | 中国科学院理化技术研究所 | A kind of self-supporting Janus photon crystal material and its preparation method and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101655610A (en) * | 2009-09-11 | 2010-02-24 | 中国科学院长春应用化学研究所 | Preparation method of inverse opal hydrogel photonic crystal with hybridized structure |
| CN103282387A (en) * | 2011-03-14 | 2013-09-04 | 旭化成化学株式会社 | Organic/inorganic composite, manufacturing method therefor, organic/inorganic composite film, manufacturing method therefor, photonic crystal, coating material, thermoplastic composition, microstructure, optical material, antireflection member, and optical lens |
| CN103103601A (en) * | 2011-11-10 | 2013-05-15 | 中国科学院化学研究所 | Method for preparing crack-free photonic crystal on surface of super-hydrophobic organism or super-hydrophobic imitation organism |
| CN105384176A (en) * | 2015-11-04 | 2016-03-09 | 北京服装学院 | Prussian blue composite photonic crystal and preparing method and application thereof |
| CN109853040A (en) * | 2019-01-30 | 2019-06-07 | 中国科学院理化技术研究所 | A kind of self-supporting Janus photon crystal material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 《对UV和CN-响应的反蛋白石结构功能材料研究》;李雪松;《中国优秀硕士学位论文全文数据库》;20110715(第07期);第13-31页 * |
| 李雪松.《对UV和CN-响应的反蛋白石结构功能材料研究》.《中国优秀硕士学位论文全文数据库》.2011,(第07期),第13-31页. * |
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